Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

• the present invention relates to a thermosetting silicone rubber composition having excellent antistatic performance.
• thermosetting silicone rubber has an at-vulcanization step of, for example, 200 ° C. for 4 hours after the primary curing in order to further remove the curing agent decomposition product and further cure.
• a technique having such a high heat resistance it has been proposed to blend a lithium salt as disclosed in Japanese Patent Application Laid-Open No. 2000-0625.
• Lithium salts have solid or powdery properties. It is important for an antistatic product to exhibit an antistatic effect on its surface, and such a solid substance has a drawback in that it takes time to manifest its effect. Furthermore, from the viewpoint of quality, the dispersion state is likely to be different, and it is difficult to obtain stable quality.
• thermosetting silicone rubber Japanese Patent Application Laid-Open No. 2 005-3 4 4 100
• a combination with a polyether-modified organohydrogen polysiloxane In the ionic liquid that is said to be limited to the addition reaction and is said to exceed the force of 1000, it is not shown what kind of substance is compatible with the silicone polymer.
• the ionic liquid having a low sexual property or characteristic brings about the effects of the present invention in a very small amount. Nor does it mention compatibility.
• the amount of the ionic liquid is large, and even if an expensive ionic liquid is used, it is not suitable for commercial use. Disclosure of the invention
• the present invention is intended to solve the above-mentioned problems of the prior art, and has an antistatic property even when high temperature at vulcanization is carried out, and further, for a long time against a silicone polymer that is poorly compatible with ionic substances.
• An object of the present invention is to provide a thermosetting silicone rubber composition capable of stably providing antistatic performance over a wide range.
• the present inventor has found a specific small amount of a specific ionic substance to the thermosetting silicone rubber.
• the inventors have found that addition is extremely effective for achieving the above object, and have completed the present invention.
• thermosetting silicone rubber 100 parts by weight
• B Add ionic substance 0.05 to 1000ppm with anion component bis (trifluoromethanesulfonyl) imide and poorly water-soluble or water-insoluble This is a thermosetting silicone rubber composition.
• thermosetting silicone rubber composition having excellent antistatic performance even after carrying out atto vulcanization at a high temperature for a long time, and further to be compatible with ionic substances.
• a thermosetting silicone rubber composition capable of stably imparting antistatic performance to a poor silicone polymer over a long period of time can be provided.
• an ionic liquid is used as the ionic substance, the surface potential is quickly lowered, so the effect is faster than in the case of solid lithium salts and the like, and it is added in comparison with the solid ionic substance. This makes it possible to reduce the amount and to maintain the translucent appearance unique to silicone rubber (especially without yellowing).
• the thermosetting silicone rubber of component (A) is composed of a polyorganosiloxane base polymer, a curing agent, and various known additives such as a filler used as necessary.
• a polyorganosiloxane base polymer those generally known can be used
• the organic group in the polyorganosiloxane base polymer is a monovalent substituted or unsubstituted hydrocarbon group, such as a methyl group or an ethyl group.
• the ru group is frequently used because of its synthetic properties.
• polydiorganosiloxanes in which at least two of the organic groups bonded to the silicon atom in one molecule are vinyl groups are common, and linear ones are particularly preferably used, but are not limited thereto.
• thermosetting silicone rubber of the present invention can be obtained by applying a known silicone rubber curing mechanism, and can be cured by crosslinking with an organic peroxide or by addition reaction. Is common.
• a commercially available organic peroxide can be used as the curing agent used for crosslinking of the organic peroxide, such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methyl.
• Benzyl peroxide 0-methyl benzoyl peroxide, dicumyl peroxide, cumino tert-butyl peroxide, 2, 5 — dimethylolene 2, 5 — dimethyl pentenole penoleoxy
• Various organic peroxide vulcanizing agents such as xanthone and di-t-butinolepenoloxide are used, especially dicumyl peroxide, cumyl t-butyl peru Preferred are xoxide, 2,5-dimethinole 2,5-di-t-butinolepenole, xyhexane and di-tbutinorepenoleside.
• organic peroxide vulcanizing agents can be used as one kind or a mixture of two or more kinds.
• the compounding amount of the organic peroxide as the curing agent is generally in the range of 0.05 to 10 parts by weight per 100 parts by weight of the silicone base polymer.
• a platinum catalyst such as chloroplatinic acid, platinum olefin complex, platinum bursiloxane complex, platinum black, or platinum triphenylphosphine complex is used as a curing catalyst.
• the cross-linking agent polydiorganosiloxane having an average of at least two hydrogen atoms bonded to a silicon atom per molecule is used.
• the amount of the curing catalyst is preferably in the range of 0.1 to 1000 ppm in terms of platinum element relative to the base polymer.
• the amount of the curing catalyst is less than 0.1 ppm as the amount of platinum element, curing will not proceed sufficiently, and if it exceeds lOOOOppm, the curing rate will be particularly improved. I can't wait.
• the amount of the crosslinking agent is preferably such that the number of hydrogen atoms bonded to the silicon atom in the crosslinking agent is 0.5 to 4.0 with respect to one alkenyl group in the base polymer, More preferably, the amount is 1.0 to 3.0. When the amount of hydrogen atoms is less than 0.5, curing of the composition does not proceed sufficiently, the hardness of the composition after curing decreases, and the amount of hydrogen atoms decreases to 4.0. If exceeded, the physical properties and heat resistance of the cured composition will be reduced.
• additives that are blended as necessary include fillers, pigments, heat resistance improvers, flame retardants, and the like.
• reinforcing silica it is preferable to mix reinforcing silica as an additive.
• reinforcing silica fumed silica, dry silica such as arc silica; precipitated silica, wet silica such as silica air mouth gel;
• examples include hydrophobic silica treated with organic silicon compounds such as hexamethyldisilazane, trimethylchlorosilane, dimethyldichlorosilane, trimethylmethoxysilane, and octamethylcyclotetrasiloxane. Hydrophobized silica is preferred.
• reinforcing silica has a specific surface area of usually 5 O m 2 / g or more, preferably 1 0 0 ⁇ 7 0 O mVg, more preferably 1 3 0 ⁇ 5 0 O m 2 / g is used.
• the reinforcing silica is blended in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the base polymer. If the amount is less than 1 part by weight, the reinforcing property is not sufficiently improved. If the amount exceeds 100 parts by weight, the compounding becomes difficult and the physical properties of the rubber are also affected.
• fillers include pulverized quartz powder, clay, calcium carbonate, diatomaceous earth, and titanium dioxide.
• heat resistance improver include iron oxide, cerium oxide, cerium hydroxide, and iron octylate.
• release agents such as saturated aliphatic hydrocarbons such as isoparaffin, fatty acid metal salts, fatty acid amides, foaming agents such as azodicarbonamide, azobisisobutyronitrile, and the like can also be added.
• the (B) ionic substance used in the present invention is an ionic substance whose anion component is bis (trifnoleolomethanesulfonyl) imide, and is poorly water-soluble or water-insoluble.
• anionic and cation components the purpose of this study is to use ionic substances that are bis (trifluoromethanesulfonyl) imide and are poorly water-soluble or water-insoluble. It is extremely excellent for obtaining the effect.
• the decomposition temperature is 220 ° C or higher.
• 1-butyl-3-methylimidazolium is preferable.
• Bis (trifluoromethanesulfonyl) imidazole 3-methyl-1-monopropylpyridinium bis (trifluoromethanesulfonyl) imide, N-butynole 3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-dimethylpyrrolidinium bis (Trifluoromethanesulfonyl) imidazole, etc., most preferably N-petite Rheum 3-methylpyridinium 'pistrifluoromethanesulfonimide or 1-butyl-1-1-methylolpyrrolidinium bis (trifluoromethanesulfonyl) imide.
• the ionic liquid has at least one alkenyl group on its cation, so that the ionic liquid having poor compatibility can be retained in the silicone rubber composition system for a long period of time.
• the alkenyl group is an aliphatic unsaturated hydrocarbon group such as a bur group, a valinole group, a methyl bur group, a propenyl group, a butyr group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclobutenyl group.
• Lium 'bis (trifluoromethanesulfonyl) imido examples include diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, and most preferred is diallyldimethylammonium bis (trifluoromethanesulfoninole) imide.
• the lithium salt lithium bis (trifluoromethanesulfonyl) imide is an ionic liquid such as 1-butyl-1,3-methylpyridine, 1-ium, trifunoleolomethanesulfonate, 1-ethyl-3-methylimidazo.
• Examples include Ryumu tetrafluoroborate.
• the amount of component (B) is 0.05 to 1000 ppm. If it is less than 0.05 ppm, the antistatic effect is not sufficient, and even if it exceeds lOOOppm, the effect is saturated and not only the characteristics inherent to silicone rubber cannot be maintained, but also it is commercially disadvantageous. There's a problem.
• a particularly preferred blending amount is 10 ppm or less.
• polyorganosiloxane in particular, ionic substance having poor compatibility with dimethyl polysiloxane, which is commonly used commercially, particularly bleed-screening ionic liquid outside the system.
• (C) polyorganosiloxane containing perfluoroalkyl group It is preferable to add 001 to 10 parts by weight (vs. 100 parts by weight of component (A)).
• the perfluoroalkyl group-containing polyorganosiloxane of component (C) may be any polyorganosiloxane containing a perfluoroalkyl group. Polyorganosiloxanes having one are known.
• Component (c) may be in any form such as linear, cyclic or branched, but is generally linear, and may have a hydroxyl group or an alkoxy group at the terminal group.
• the viscosity is preferably less than 1 00 0 0 0 c St, more preferably less than 1 0 0 0 c St. When the viscosity is higher than 1 0 0 0 0 c St, the difference in viscosity from the component (B) becomes large and mixing becomes difficult.
• (C) perfluoroalkyl group-containing polyorganosiloxane is added after preparing a mixture in which an ionic substance with component (B) is mixed at a ratio of 0.1 to 50%. Is preferred.
• the reinforcing silica described above is blended in the composition in a state where the ionizable substance of the component (B) or the mixture of the component (B) and the component (C) is supported. That is. This facilitates the dispersion of the component (B) in the composition and improves the retention in the system.
• thermosetting silicone rubber composition of the present invention is excellent in transparency, a duplicate product is produced with a cover of a portable music player, a portable game, a mobile phone, a controller of a game machine, or a urethane resin. It is preferably used for silicone rubber molds used for coating, and silicone rubber coating on fabrics.
• this base compound is water-insoluble and N-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidine is a liquid at room temperature with a decomposition temperature of 29 ° C. dry silica de lOppm and a specific surface area of 150 meters 2 / g (Made by Nippon Aerosil Co., Ltd.) 0.02 part was blended and supported on a filler and mixed. Then, 1.0 parts of vulcanizing agent (TC-8, Momentive 'Performance Materials Japan, Inc., containing 2.
• TC-8 Momentive 'Performance Materials Japan, Inc.
• diallyl dimethylammonium bis is a liquid that is slightly water-soluble and has a decomposition temperature of 2700 ° C.
• a rubber sheet was obtained in the same manner as in Example 1 except that (trifluoromethanesulfonyl) imide was used.
• a rubber sheet was obtained in the same manner as in Example 1 except that N-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide was not added.
• N-butynole 3-methinolepyridinium bis (trifluoromethanesulfonyl) imide is easily water soluble and liquid at room temperature with a decomposition temperature of 3500 ° C.
• a rubber sheet was obtained in the same manner as in Example 1 except that imidazolium 'tetrafluoroborate was used.
• Perfluoroalkyl group-containing polyorganosiloxane with a viscosity of 150 c St (containing 3 O mol% of methyl trifluoropropyl group siloxane knit, the other is composed of dimethyl siloxane kiznit, and has direct hydroxyl groups at both ends.
• (Chain polymer) Dissolved in 1 part of N-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, which is slightly water-soluble and liquid at room temperature with a decomposition temperature of 2900 ° C, in 100 parts The liquid was prepared.
• a rubber sheet was obtained in the same manner as in Example 2 except that 0.1 part of this solution was added instead of N-butyl_3_methylpyridinium bis (trifluoromethanesulfonyl) imide. .
• Perfluoroalkyl group-containing polyorganosiloxane with a viscosity of 150 c St (containing 3 O mol% of methyl trifluoropropyl group siloxane knit, the other is composed of dimethyl siloxane kiznit, and has direct hydroxyl groups at both ends.
• a rubber sheet was obtained in the same manner as in Example 4, except that fluorosilicone oil having 100% methyl trifluoropropyl units at both terminal hydroxyl groups and 100% methyl trifluoropropyl units was used.
• fluorosilicone oil having 100% methyl trifluoropropyl units at both terminal hydroxyl groups and 100% methyl trifluoropropyl units was used.
• Example 4 except that N-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide was used and diaryldimethylammonium bis (trifluoromethanesulfonyl) imide was used.
• a rubber sheet was obtained.
• Table 1 shows the results of evaluating the physical properties of the rubber sheet obtained according to the following criteria.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Related Child Applications (2)

Publications (1)

Family

ID=40824435

Family Applications (1)

Country Status (7)

Cited By (13)

Families Citing this family (7)

Citations (13)

Family Cites Families (19)

• 2008
  • 2008-12-24 TW TW097150427A patent/TWI588210B/zh active
  • 2008-12-26 KR KR1020107011093A patent/KR101463736B1/ko active IP Right Grant
  • 2008-12-26 CN CN2008801233209A patent/CN101910316B/zh active Active
  • 2008-12-26 EP EP08866020.4A patent/EP2233530B1/en active Active
  • 2008-12-26 US US12/735,083 patent/US8779072B2/en active Active
  • 2008-12-26 WO PCT/JP2008/073962 patent/WO2009084730A1/ja active Application Filing
  • 2008-12-26 JP JP2009548128A patent/JP5422394B2/ja not_active Expired - Fee Related
• 2014
  • 2014-05-27 US US14/287,492 patent/US20140275363A1/en not_active Abandoned

Patent Citations (13)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events